WO2010062527A1 - Conversion of hydrofluorochloropropanes to fluoropropenes - Google Patents

Conversion of hydrofluorochloropropanes to fluoropropenes Download PDF

Info

Publication number
WO2010062527A1
WO2010062527A1 PCT/US2009/061828 US2009061828W WO2010062527A1 WO 2010062527 A1 WO2010062527 A1 WO 2010062527A1 US 2009061828 W US2009061828 W US 2009061828W WO 2010062527 A1 WO2010062527 A1 WO 2010062527A1
Authority
WO
WIPO (PCT)
Prior art keywords
chloropropane
fluoropropene
selectivity
hydrofluorochloropropane
temperature
Prior art date
Application number
PCT/US2009/061828
Other languages
English (en)
French (fr)
Inventor
Mario Joseph Nappa
Original Assignee
E. I. Du Pont De Nemours And Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by E. I. Du Pont De Nemours And Company filed Critical E. I. Du Pont De Nemours And Company
Priority to KR1020177007120A priority Critical patent/KR101938099B1/ko
Priority to PL09752568T priority patent/PL2346800T3/pl
Priority to KR1020187033522A priority patent/KR20180127527A/ko
Priority to JP2011533364A priority patent/JP5513513B2/ja
Priority to ES09752568T priority patent/ES2391611T3/es
Priority to CA2736437A priority patent/CA2736437A1/en
Priority to MX2011004319A priority patent/MX2011004319A/es
Priority to RU2011121361/04A priority patent/RU2011121361A/ru
Priority to KR1020197020662A priority patent/KR20190086789A/ko
Priority to CN200980142737.4A priority patent/CN102197012B/zh
Priority to BRPI0914365A priority patent/BRPI0914365A2/pt
Priority to EP09752568A priority patent/EP2346800B1/en
Publication of WO2010062527A1 publication Critical patent/WO2010062527A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C21/00—Acyclic unsaturated compounds containing halogen atoms
    • C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
    • C07C21/18—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds containing fluorine

Definitions

  • compositions that meet both low ozone depletion standards as well as having low global warming potentials.
  • Certain hydrofluoroolefins are believed to meet both goals.
  • manufacturing processes that provide halogenated hydrocarbons and fluoroolefins that contain no chlorine that also have a low global warming potential.
  • Described is a method for producing fluoropropenes of formula CF 3 CX CX2 wherein each X is F or H, at least one X is H, and at least one X is F, comprising pyrolyzing a hydrofluorochloropropane of formula CF3CXYCX2Y, wherein each X is F or H, at least one X is H, and at least one X is F, and one Y is Cl and the other Y is H, in the gas-phase in a reaction vessel, maintained at a temperature high enough to effect the pyrolysis of said hydrofluorochloropropane to said fluoropropene, wherein the selectivity for the production of the fluoropropene is at least 80%, in the absence of a catalyst.
  • Described is a method for producing fluoropropenes of formula CF 3 CX CX2 wherein each X is F or H, at least one X is H, and at least one X is F, comprising pyrolyzing a hydrofluorochloropropane of formula CF3CXYCX2Y, wherein each X is F or H, at least one X is H, and at least one X is F, and one Y is Cl and the other Y is H, in the gas-phase in a reaction vessel, maintained at a temperature high enough to effect the pyrolysis of said hydrofluorochloropropane to said fluoropropene, wherein the selectivity for the production of the fluoropropene is at least 80%, in the absence of a catalyst.
  • reaction vessel refers to any vessel in which the reaction may be performed in either a batchwise mode, or in a continuous mode. Suitable vessels include batch reactor vessels, or tubular reactors.
  • the reaction vessel is comprised of materials which are resistant to corrosion including stainless steel, Hastelloy, Inconel, Monel, gold, or gold-lined or quartz.
  • percent selectivity is defined as the weight of a desired product formed, as a fraction of the total amount of the products formed in the reaction, and excluding the starting chlorofluorocarbon.
  • percent conversion is defined as 100%, less the weight percent of starting hydrofluorochloropropane in the effluent from the reaction vessel.
  • the hydrochlorofluoropropane described herein has the formula CF3CXYCX2Y, wherein each X is F or H, at least one X is H, and at least one X is F, and one Y is Cl and the other Y is H.
  • Representative hydrochlorofluoropropanes include 1 ,1 ,1 ,2-tetrafluoro-2-chloropropane, 1 ,1 ,1 ,2-tetrafluoro-3-chloropropane, 1 ,1 ,1 ,3-tetrafluoro-2-chloropropane, 1 ,1 ,1 ,3-tetrafluoro-3-chloropropane, 1 ,1 ,1 ,2,3-pentafluoro-2- chloropropane, 1 ,1 ,1 ,2,3-pentafluoro-3-chloropropane, 1 ,1 ,1 ,3,3- pentafluoro-2-chloropropane and 1 ,1 ,1 ,3,3-pentafluoro-3-chloropropane.
  • Representative fluoropropenes include 2,3,3,3-tetrafluoropropene, 1 ,3,3,3-tetrafluoropropene, 1 ,2,3,3, 3-pentafluoropropene and 1 ,1 ,3,3,3- pentafluoropropene.
  • the hydrochlorofluoropropane is 1 ,1 ,1 ,2- tetrafluoro-2-chloropropane and the fluoropropene is 2,3,3,3- tetrafluoropropene.
  • the hydrochlorofluoropropane is 1 ,1 ,1 ,2-tetrafluoro-3-chloropropane and the fluoropropene is 2,3,3,3- tetrafluoropropene.
  • the hydrochlorofluoropropane is 1 ,1 ,1 ,3-tetrafluoro-2-chloropropane and the fluoropropene is 1 ,3,3,3-tetrafluoropropene.
  • the hydrochlorofluoropropane is 1 ,1 ,1 ,3-tetrafluoro-3-chloropropane and the fluoropropene is 1 ,3,3,3-tetrafluoropropene.
  • the hydrochlorofluoropropane is 1 ,1 ,1 ,2,3-pentafluoro-2- chloropropane and the fluoropropene is 1 ,2,3,3,3-pentafluoropropene.
  • the hydrochlorofluoropropane is 1 ,1 ,1 ,2,3- pentafluoro-3-chloropropane and the fluoropropene is 1 ,2,3,3,3- pentafluoropropene.
  • the hydrochlorofluoropropane is 1 ,1 ,1 ,3,3-pentafluoro-2-chloropropane and the fluoropropene is 1 ,1 ,3,3,3-pentafluoropropene.
  • the hydrochlorofluoropropane is 1 ,1 ,1 ,3,3-pentafluoro-3- chloropropane and the fluoropropene is 1 ,1 ,3,3,3-pentafluoropropene.
  • fluoropropenes are prepared by thermal dehydrochlorination of hydrochlorofluoropropanes. This reaction occurs selectively, in the absence of a catalyst.
  • a hydrochlorofluoropropane is introduced into a reaction vessel wherein the temperature is maintained at a temperature high enough to effect the thermal dehydrochlorination of the hydrochlorofluoropropane.
  • the temperature is high enough to effect the thermal dehydrochlorination of the hydrochlorofluoropropane to a percent conversion of at least 50%.
  • the temperature is high enough to effect the thermal dehydrochlorination of the hydrochlorofluoropropane to a percent conversion of at least 65%.
  • the temperature is high enough to effect the thermal dehydrochlorination of the hydrochlorofluoropropane to a percent conversion of at least 80%.
  • the temperature is high enough to effect the thermal dehydrochlorination of the hydrochlorofluoropropane to a percent conversion of at least 70% for at least 12 hours of continuous operation.
  • the hydrochlorofluoropropane is introduced into a reaction vessel wherein the temperature is maintained at a temperature in the range of from about 500 0 C to about 700 0 C. In another embodiment, the temperature of the reaction vessel is maintained in the range from about 500 0 C to about 650 0 C. In yet another embodiment, the temperature of the reaction vessel is maintained at a temperature high enough to effect the the pyrolysis of the hydrochlorofluoropropane to fluoropropene with a selectivity of 80% or greater. In yet another embodiment, the temperature of the reaction vessel is maintained at a temperature high enough to effect the pyrolysis of the hydrochlorofluoropropane to the fluoropropene with a selectivity of 85% or greater. In one embodiment, the reaction vessel is comprised of materials which are resistant to corrosion. In one embodiment, these materials comprise alloys, such as stainless steel, Hastelloy, Inconel, Monel, and gold, gold-lined or quartz.
  • the hydrochlorofluoropropane is preheated in a vaporizer to a temperature of from about 30 0 C to about 100 0 C. In another embodiment, the hydrochlorofluoropropane is preheated in a vaporizer to a temperature of from about 30 0 C to about 80 0 C.
  • an inert diluent gas is used as a carrier gas for the hydrochlorofluoropropane.
  • the carrier gas is selected from nitrogen, argon, helium or carbon dioxide.
  • the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having” or any other variation thereof, are intended to cover a non-exclusive inclusion.
  • a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
  • “or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).
  • HFC-244bb is 2-chloro-1 ,1 ,1 ,2-tetrafluoropropane
  • HFO-1234yf is 2,3,3,3-tetrafluoropropene
  • HCFO-1233xf is 2-chloro-3,3,3-trifluoropropene
  • Example 1 demonstrates the conversion of 2-chloro-1 ,1 ,1 ,2- tetrafluoropropane to 2,3,3,3-tetrafluoropropene in the absence of a catalyst.
  • HFC-244bb was fed at 0.52 ml/hour through a vaporizer set at 4O 0 C using a N 2 sweep of 2.4 seem (4.0 x 10 ⁇ 8 m 3 ).
  • the reactor effluent was analyzed using an on-line GCMS, with the results being reported in mole percent. Results for percent conversion, percent selectivity, and operating temperature are reported in Table 1 , below. Table 1
  • Example 2 demonstrates the conversion of 2-chloro-1 ,1 ,1 ,2- tetrafluoropropane to 2,3,3,3-tetrafluoropropene in the absence of a catalyst.
  • Example 3 demonstrates the conversion of 2-chloro-1 ,1 ,1 ,2- tetrafluoropropane to 2,3,3,3-tetrafluoropropene in the absence of a catalyst in a gold-lined tube.
  • Comparative Example 1 demonstrates the dehydrochlorination of 2- chloro-1 ,1 ,1 ,2-tetrafluoropropane in the presence of an activated carbon catalyst.
  • Table 4 show the performance of this process with an activated carbon catalyst to make HFO-1234yf via HCI elimination over the period of 15 hours of operation .

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
PCT/US2009/061828 2008-10-27 2009-10-23 Conversion of hydrofluorochloropropanes to fluoropropenes WO2010062527A1 (en)

Priority Applications (12)

Application Number Priority Date Filing Date Title
KR1020177007120A KR101938099B1 (ko) 2008-10-27 2009-10-23 하이드로플루오로클로로프로판의 플루오로프로펜으로의 전환
PL09752568T PL2346800T3 (pl) 2008-10-27 2009-10-23 Przekształcanie wodorofluorochloropropanów do fluoropropenów
KR1020187033522A KR20180127527A (ko) 2008-10-27 2009-10-23 하이드로플루오로클로로프로판의 플루오로프로펜으로의 전환
JP2011533364A JP5513513B2 (ja) 2008-10-27 2009-10-23 ヒドロフルオロクロロプロパンのフルオロプロペンへの変換
ES09752568T ES2391611T3 (es) 2008-10-27 2009-10-23 Conversión de hidrofluorocloropropanos a fluoropropenos
CA2736437A CA2736437A1 (en) 2008-10-27 2009-10-23 Conversion of hydrofluorochloropropanes to fluoropropenes
MX2011004319A MX2011004319A (es) 2008-10-27 2009-10-23 Conversion de hidrofluorocloropropanos a fluoropropenos.
RU2011121361/04A RU2011121361A (ru) 2008-10-27 2009-10-23 Превращение гидрофторхлорпропанов в фторпропены
KR1020197020662A KR20190086789A (ko) 2008-10-27 2009-10-23 하이드로플루오로클로로프로판의 플루오로프로펜으로의 전환
CN200980142737.4A CN102197012B (zh) 2008-10-27 2009-10-23 氢氟氯丙烷向氟丙烯的转化
BRPI0914365A BRPI0914365A2 (pt) 2008-10-27 2009-10-23 ''método de produção de fluoropropeno''
EP09752568A EP2346800B1 (en) 2008-10-27 2009-10-23 Conversion of hydrofluorochloropropanes to fluoropropenes

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US10858508P 2008-10-27 2008-10-27
US61/108,585 2008-10-27

Publications (1)

Publication Number Publication Date
WO2010062527A1 true WO2010062527A1 (en) 2010-06-03

Family

ID=41832362

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2009/061828 WO2010062527A1 (en) 2008-10-27 2009-10-23 Conversion of hydrofluorochloropropanes to fluoropropenes

Country Status (11)

Country Link
EP (1) EP2346800B1 (enrdf_load_stackoverflow)
JP (1) JP5513513B2 (enrdf_load_stackoverflow)
KR (4) KR20190086789A (enrdf_load_stackoverflow)
CN (2) CN102197012B (enrdf_load_stackoverflow)
BR (1) BRPI0914365A2 (enrdf_load_stackoverflow)
CA (1) CA2736437A1 (enrdf_load_stackoverflow)
ES (1) ES2391611T3 (enrdf_load_stackoverflow)
MX (1) MX2011004319A (enrdf_load_stackoverflow)
PL (1) PL2346800T3 (enrdf_load_stackoverflow)
RU (1) RU2011121361A (enrdf_load_stackoverflow)
WO (1) WO2010062527A1 (enrdf_load_stackoverflow)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014530213A (ja) * 2011-09-30 2014-11-17 ハネウェル・インターナショナル・インコーポレーテッド ２，３，３，３−テトラフルオロプロペンの製造方法
US10301236B2 (en) 2015-05-21 2019-05-28 The Chemours Company Fc, Llc Hydrofluorination of a halogenated olefin with SbF5 in the liquid phase

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20140110029A (ko) * 2012-01-09 2014-09-16 이 아이 듀폰 디 네모아 앤드 캄파니 반응기 패시베이션 방법
CN105753641B (zh) * 2014-12-13 2018-08-31 西安近代化学研究所 1,3,3,3-四氟丙烯的制备方法
CN108640812A (zh) * 2018-06-21 2018-10-12 岳阳景嘉化工有限公司 一种2，3-二氯丙烯的合成方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5516946A (en) * 1994-06-29 1996-05-14 E. I. Du Pont De Nemours And Company Producing CF3 CH2 CF3 and/or CF3 CH=CF2 by the conversion of fluorinated ethers
US20060094911A1 (en) * 2004-10-29 2006-05-04 Rao Velliyur N M Noncatalytic manufacture of 1,1,3,3,3-pentafluoropropene from 1,1,1,3,3,3-hexafluoropropane
WO2008002499A2 (en) * 2006-06-27 2008-01-03 E. I. Du Pont De Nemours And Company Tetrafluoropropene production processes

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7230146B2 (en) * 2003-10-27 2007-06-12 Honeywell International Inc. Process for producing fluoropropenes
US7592494B2 (en) * 2003-07-25 2009-09-22 Honeywell International Inc. Process for the manufacture of 1,3,3,3-tetrafluoropropene
US7091388B2 (en) * 2003-09-26 2006-08-15 Honeywell International Inc. Method of making 1,1,3,3,3-pentafluoropropene
US8084653B2 (en) * 2004-04-29 2011-12-27 Honeywell International, Inc. Method for producing fluorinated organic compounds
MY155312A (en) * 2004-12-21 2015-09-30 Honeywell Int Inc Stabilized iodocarbon compositions
US8071825B2 (en) * 2006-01-03 2011-12-06 Honeywell International Inc. Method for producing fluorinated organic compounds
SI2546224T2 (sl) * 2006-01-03 2023-10-30 Honeywell International Inc. Postopek izdelave fluoriranih organskih spojin

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5516946A (en) * 1994-06-29 1996-05-14 E. I. Du Pont De Nemours And Company Producing CF3 CH2 CF3 and/or CF3 CH=CF2 by the conversion of fluorinated ethers
US20060094911A1 (en) * 2004-10-29 2006-05-04 Rao Velliyur N M Noncatalytic manufacture of 1,1,3,3,3-pentafluoropropene from 1,1,1,3,3,3-hexafluoropropane
WO2008002499A2 (en) * 2006-06-27 2008-01-03 E. I. Du Pont De Nemours And Company Tetrafluoropropene production processes

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014530213A (ja) * 2011-09-30 2014-11-17 ハネウェル・インターナショナル・インコーポレーテッド ２，３，３，３−テトラフルオロプロペンの製造方法
US10301236B2 (en) 2015-05-21 2019-05-28 The Chemours Company Fc, Llc Hydrofluorination of a halogenated olefin with SbF5 in the liquid phase
US10988422B2 (en) 2015-05-21 2021-04-27 The Chemours Company Fc, Llc Hydrofluoroalkane composition
US11008267B2 (en) 2015-05-21 2021-05-18 The Chemours Company Fc, Llc Hydrofluoroalkane composition
US11572326B2 (en) 2015-05-21 2023-02-07 The Chemours Company Fc, Llc Method for preparing 1,1,1,2,2-pentafluoropropane
US12006274B2 (en) 2015-05-21 2024-06-11 The Chemours Company Fc, Llc Compositions including olefin and hydrofluoroalkane

Also Published As

Publication number Publication date
PL2346800T3 (pl) 2013-01-31
EP2346800A1 (en) 2011-07-27
ES2391611T3 (es) 2012-11-28
CN104262078A (zh) 2015-01-07
KR20180127527A (ko) 2018-11-28
CA2736437A1 (en) 2010-06-03
BRPI0914365A2 (pt) 2015-10-20
CN102197012B (zh) 2014-10-01
JP5513513B2 (ja) 2014-06-04
KR101938099B1 (ko) 2019-01-11
KR20170032492A (ko) 2017-03-22
MX2011004319A (es) 2011-05-30
JP2012506863A (ja) 2012-03-22
RU2011121361A (ru) 2012-12-10
CN102197012A (zh) 2011-09-21
EP2346800B1 (en) 2012-08-29
KR20190086789A (ko) 2019-07-23
KR20110089307A (ko) 2011-08-05

Similar Documents

Publication Publication Date Title
US8445735B2 (en) Conversion of 2-chloro-1,1,1,2-tetrafluoropropane to 2,3,3,3-tetrafluoropropene
US7833434B2 (en) Tetrafluoropropene production processes
EP3336073B1 (en) Method for producing fluorinated organic compounds
KR101914184B1 (ko) 히드로클로로플루오로카본의 촉매적 탈염화수소화
EP3395790B1 (en) Synthesis of 1,1,3-trichloro-1-propene
EP3686178A1 (en) Composition comprising hydrohaloalkene, hf and fluorination catalyst
EP2630107B1 (en) Process for the manufacture of 2-chloro-3,3,3-trifluropropene by gas phase fluorination of pentachloropropane
US8697922B2 (en) Conversion of 2-chloro-1,1,1,2-tetrafluoropropane to 2,3,3,3-tetrafluoropropene
EP2346800B1 (en) Conversion of hydrofluorochloropropanes to fluoropropenes
MX2013009579A (es) Deshidrocloracion catalitica selectiva de hidroclorofluorocarburo.
US9296669B2 (en) Process for reactor passivation
EP3820834B1 (en) Methods for an integrated 2,3,3,3-tetrafluoropropene manufacturing process
HK1162167A (en) Conversion of hydrofluorochloropropanes to fluoropropenes

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200980142737.4

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 09752568

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2736437

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 2108/DELNP/2011

Country of ref document: IN

WWE Wipo information: entry into national phase

Ref document number: 2009752568

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2011533364

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: MX/A/2011/004319

Country of ref document: MX

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20117012022

Country of ref document: KR

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 2011121361

Country of ref document: RU

ENP Entry into the national phase

Ref document number: PI0914365

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20110426